The local electronic environments and energy storage properties of lithium electrodes are investigated through inelastic electron scattering and electrochemical measurements. Experimental and computational methods are developed to characterize the electronic structure of lithiated compounds during electrochemical cycling. An electrochemical investigation of new lithium alloys has led to a better understanding of the thermodynamics, kinetics, and mechanical properties of nanostructured materials. These studies have also inspired the development of new anode materials for rechargeable lithium batteries. One of the large controversies regarding lithium cathodes concerns the arrangement of the local electronic environments in the host material and how these environments are affected by lithium intercalation. To investigate this issue, the core edges of the 3d transition-metal oxides were studied using electron energy-loss spectrometry. A number of techniques were developed to better understand how characteristics of the electronic structure are reflected in the core edge and near-edge structure of metal oxides. An empirical relationship is established between the transition-metal L23 white line intensity and the transition-metal 3d occupancy. In addition, the near-edge structure of the oxygen K-edge was used to investigate the 2p electron density about the oxygen ions. The results of these investigations were used to study charge compensation in lithiated transition-metal oxides (e.g., LiCoO2 and LiNi0.8Co0.2O2) during electrochemical cycling. These results show a large increase in state occupancy of the oxygen 2p band during lithiation, suggesting that much of the lithium 2s electron is accommodated by the anion. Ab initio calculations of the oxygen 2p partial density of states curves confirm the increase in unoccupied states that accompany lithium extraction. In contrast with the large changes observed in the oxygen K-edge, much smaller changes were observed in the transition-metal L23 white lines. Surprisingly, for layered LiCoO2 and Li(Ni, Co)O2, the transition-metal valence changes little during the charge compensation accompanying lithiation. These results have led to a better understanding of intercalation hosts and the role of oxygen in these layered structures. Recent demand for alternatives to graphitic carbon for lithium anodes motivated an investigation into novel binary lithium alloys. The large volume expansions associated with lithium insertion is known to generate tremendous microstructural damage, making most alloys unsuitable for rechargeable lithium batteries. Electrodes of nanostructured lithium alloys were prepared in an attempt to mitigate the particle decrepitation that occurs during cycling and to shorten diffusion times for lithium. Anodes of silicon and germanium were prepared in thin film form as nanocrystalline particles (10 nm mean diameter) and as continuous amorphous thin films (60-250 nm thick). These nanostructured materials exhibited stable capacities up to six times larger than what is found in graphitic carbons, which are currently the industry standard. In addition, these electrodes do not suffer from particle decrepitation and therefore exhibit excellent cycle life. Nanocrystalline electrodes of silicon and germanium were found to transform into a glassy phase via an electrochemically driven solid-state amorphization during the initial alloying. The disordered structure is believed to assuage strains of intercalation by bypassing multiple crystallographic phases. However, the primary reason for the improved reversibility in these electrodes is attributed to the nanoscale dimensions, which circumvent conventional mechanisms of mechanical deterioration. Nanostructured Li-Si and Li-Ge exhibit the highest reversible electrochemical capacities yet reported for an alloy electrode. Future investigations of the local electronic environments in cathodes could be extended to include more complicated systems such as Li(Ni, Mn)O2 and Li(Fe, X)PO4. Our results suggest that the electronic stability of the metal ion is necessary to maintain a prolonged cycle life. Therefore, an understanding of charge compensation in these complex oxides will be important for understanding new cathode materials. The electronic environments will also be a critical component in the development of alternative anodes, such as binary and ternary lithium alloys. Chemical and valence maps will be used to determine how the lithium is distributed and how its chemical potential varies throughout the electrode. In addition, a better understanding of the thermodynamics, kinetics, and mechanical properties of lithium hosts will be necessary for the development of lithium electrodes with high capacities and high rate capabilities.